Atomic Layer Deposition of Chalcogenide Thin Films...Xu, J. et al.Atomic layer deposition of...
Transcript of Atomic Layer Deposition of Chalcogenide Thin Films...Xu, J. et al.Atomic layer deposition of...
PUBLICATION REVIEWON ULTRATECH ALD SYSTEMS
Atomic Layer Depositionof Chalcogenide Thin Films
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09.10.2015
Highlights
q BenefitsofALDfornano-manufacturingofchalcogenidesq Atomiclevelthicknesscontrolq Depositionon3DnanostructuresusingExpoModeq Controlofcompositioninmulticomponentsulfidesq Widerangeofsulfidesdepositedbycustomers:q Cu2S,Sb2S3,In2S3,SnS,ZnS,PbS,Cu2ZnSnS4 forPVsq MoS2 for2Dmaterialsq CNThasextensiveR&Dandmanufacturingexperiencewithsulfides,e.g.,
Zn(O,S)andhandlingofH2Sq Keyusers:ArgonneNationalLab,StanfordU.,U.ofHamburg,U.of
Michigan
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Introductionq Greatinterestinsulfides for
photovoltaics,photonics, catalysisq RequiresH2Sq Chalcogenidephotovoltaics
§ Absorber§ bandgapsandenergylevelsmore
suitablethanoxides§ 31-34%efficiencyat1-1.6eV§ CZTSquaternarysynthesizedforfirst
time§ Cu2SstabilizedbythinALDoxides
§ Buffer/Emitter§ In2S3,ZnS,andCdS, andZn(O,S)
q EnergyStorage§ Cu2S/CNTcathodes@260mAhg-1
§ Li2S@800mAhg-1
q Photonics§ ZnSforTFELdisplays(firstALD
industrialapplication)
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1.Dasgupta,N.P.,etal.,AccountsChem Res48,341–348(2015).
Single junction efficiency limits
ALD sulfide absorbers
CIGS- Photovoltaics
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q Absorber /buffer/TCOcombination determinesspectralcapturerange
q Maxefficiencytodateat20%q Complexheterojunction, wherebufferand
absorber interfacedeterminebandbendingandultimateefficiency
q Buffermaterial,composition, opticalproperties,andfilmuniformity arecrucial
ZnO(1-x)Sx composition
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Composition controlledbychanging thenumberofZnS/ZnOcyclesinorder tomatchgivenCIGScomposition
3.5
3.4
3.3
3.2
3.1
3.0
2.9
2.8
2.7
2.6
2.5
Ban
d Ga
p [e
V]
1.00.80.60.40.20.0
x - composition of ZnO(1-x)Snx
Quantumefficiencymeasurement
TEMcross-sectionofaCIGScellwithALDgrownZn(O,S)bufferlayer.
1.Bhargavaet.al.,JournaloftheKoreanPhysicalSociety,Vol53,No.5,,2008.2.ZimmermannU.,etal.,21stEur.PhotovoltaicSolarEnergyConference(2006),Dresden
x– compositionofZnO(1-x)Sx
Cu2ZnSnS4 (CZST)
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q Objectives§ Lowcostseminconductor (CZST)for
photovoltaic§ 1.4eVbandgap,conformality in3D§ Compositional controlofquaternary
materialsq Experimental
§ SavannahS200,Expo,H2Skit,150˚C§ Cu2S:Cu2DBA(Strem)@160˚C+1%H2S§ SnS:TDMASn+1%H2S§ ZnS:DEZ+1%H2S§ 2strategies:trilayersandnanolaminates
Thimsenetal.,ChemistryofMaterials,24(16),3188–3196(2012).doi:10.1021/cm3015463
Cu2S/SnS2/ZnStrilayer depositedonasilicontrenchwafer
InterfaceandcompositionprofileinCZST
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1.Thimsen,ChemistryofMaterials,24(16),3188–3196(2013)[Argonne]
Cu2SonSWCNT(100,200,400,600cycles)
Charge/dischargeforfirst3cyclesat1000mA/g
Cu2ScathodeforLIB
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q Objectives§ Cu2Sdepositedonsinglewall
carbonnanotubesq Experimental
§ SavannahS200at135˚C,expomode
§ CuAMD(150˚C)and1%H2S§ SWCNTfunctionalized
with9minO3
q Results§ Core-shellSWCNT-n-Cu2Sexhibits
highchargedischarge/stability§ highcapacity(260mA/g)§ >99%Coulombicefficiency
1Meng,X.,JournalofPowerSources,2015,280,621–629 [ArgonneNL]
StabilizationofCu2SforPVs
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q Cu2SPVabsorber§ abundant,nontoxic,
absorption>1E4cm-1
q IssuewithCu2S/CdSjunctionduetoCudiffusion
q S200forCu2SfromCuAMD/H2S@145˚C
q TiO2 ALDusedasCudiffusionbarrierandn-typeemittertoreplaceCdS
q 1-2Al2O3 cyclesreducecarrierconcentrationandstabilizefilmfor>2weeks
1.Riha,S.C.etalAcsApplMaterInter131010083550003 (2013).[ArgonneNL]
Carrierconcentrationfromin-situIV
PassivationofCu2SwithTiO2 &Al2O3/TiO2
In2S3 ALD
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MassGainduringIn(amd)3 /H2Scycles
Absorptioncoefficientatvaryingdep.temperatures Impactofprocesstemperatureonn-typeIn2S3
q ChalcogenidePVtoreplaceCdS
q In(amd)3 andH2SinS200q Self-limitedALDupto225˚Cq 0.89Å/cycle@150˚Cq NodetectableC,N,O
halogen (RBS/AES)
1McCarthy,R.F.,etal,AcsApplMaterInter6,12137–12145(2014).[ArgonneNL]
Referencelist
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1. Xu,J.etal. Atomiclayerdeposition ofabsorbing thinfilmsonnanostructuredelectrodesforshort-wavelengthinfraredphotosensing. Appl Phys Lett 107, 153105–5(2015).2. McCarthy,R.F.,Schaller, R.D.,Gosztola,D.J.,Wiederrecht,G.P.&Martinson,A.B.F.Photoexcited CarrierDynamicsofIn2S3ThinFilms. J.Phys.Chem.Lett. (2015).doi:10.1021/acs.jpclett.5b009353. Baryshev,S.V.,Riha,S.C.&Zinovev, A.V.SolarAbsorberCu2ZnSnS4 anditsParentMultilayersZnS/SnS2/Cu2SSynthesizedbyAtomicLayerDeposition andAnalyzedbyX-rayPhotoelectron Spectroscopy.Surf.Sci.Spectra 22, 81–99(2015).4. Riha,S.C.,Schaller,R.D.,Gosztola,D.J.,Wiederrecht,G.P.&Martinson,A.B.F.Photoexcited CarrierDynamicsofCu2SThinFilms.J.Phys.Chem.Lett. 5, 4055–4061(2014).5. Sutherland, B.R.etal. PerovskiteThinFilms viaAtomicLayerDeposition.AdvancedMaterials n/a–n/a(2014).doi:10.1002/adma.2014039656. McCarthy,R.F.,Weimer,M.S.,Emery,J.D.,Hock,A.S.&Martinson,A.B.F.Oxygen-FreeAtomicLayerDepositionofIndiumSulfide.Acs Appl MaterInter 6, 12137–12145(2014).7. Riha,S.C.etal. StabilizingCu2SforPhotovoltaicsOneAtomicLayerataTime.Acs Appl MaterInter131010083550003 (2013).doi:10.1021/am403225e8. Thimsen, E.etal. InterfacesandComposition ProfilesinMetal–SulfideNanolayers Synthesized byAtomicLayerDeposition.ChemMater 25, 313–319(2013).9. Thimsen, E.etal. AtomicLayerDeposition oftheQuaternaryChalcogenideCu2ZnSnS4.ChemMater 24, 3188–3196(2012).10. Yang,R.B.etal. PulsedVapor-Liquid-Solid GrowthofAntimony Selenide andAntimony SulfideNanowires.AdvancedMaterials 21, 3170–3174(2009).11. Dasgupta,N.P.,Walch,S.P.&Prinz,F.FabricationandCharacterizationofLeadSulfide ThinFilms byAtomicLayerDeposition.ECSTransactions 16, 29–36(2008).
SulfideworkdoneonUltratechCNTALDsystems